Electronic devices using organic small molecule semiconducting compounds

ABSTRACT

Small organic molecule semi-conducting chromophores containing a halogen-substituted core structure are disclosed. Such compounds can be used in organic heterojunction devices, such as organic small molecule solar cells and transistors.

CLAIM OF PRIORITY

This application is a continuation of U.S. patent application Ser. No.14/378,829, filed on Aug. 14, 2014, which is a U.S. National StageApplication under 35 U.S.C. § 371 of PCT/US2013/025936 filed Feb. 13,2013, which claims the benefit of U.S. Provisional Application No.61/603,039, filed Feb. 24, 2012, and to U.S. Provisional Application No.61/598,646, filed Feb. 14, 2012, each of which is incorporated byreference in its entirety.

BACKGROUND

Solution-processed organic photovoltaic devices (OPV) have emerged as apromising energy technology due to their ease of processing, low-cost,and ability to be fabricated onto light-weight flexible substrates.Polymer based OPV's have by far been the most studied, and powerconversion efficiencies (PCE's) above 6% have recently been reported forpolymer:fullerene bulk heterojunction (BHJ) devices. On the other hand,solution processed small molecule BHJ devices have received far lessattention. Such molecular heterojunctions (MHJ) have several advantagesover their polymer counterparts, in that small molecules have welldefined structures, are easily functionalized, are mono-disperse, arereadily purified, and do not suffer from batch-to-batch variations.Reports of efficient solution processed MHJ devices have recentlyemerged that have utilized merocyanine dyes, squaraine dyes, isoindigo,and diketopyrrolopyrrole based chromophores as the light harvestingdonor component with a fullerene acceptor. PCE's have reached upwards of4% for such devices. While these results are encouraging, there stillexits a need for the development of novel discrete light harvestingmaterials. Key parameters for effective small molecule donors includehaving broad and efficient optical absorption that extends into thenear-IR region to maximize photon absorption, deep HOMO levels from −5to −5.5 eV to maximize open circuit voltages, relatively planarstructures for high charge carrier mobility, high solution viscosity andsolubilizing side chains for solution to film processing. Additionally,it is important that novel structures have facile and highly tunablesyntheses to enable rapid and cheap generation of molecular libraries.

The present invention seeks to address the need for improved lightharvesting molecules and molecular heterojunction devices by providingnovel and advantageous materials and their use in such devices.

SUMMARY

In one embodiment, the present invention is directed to organicnon-polymeric semiconducting compounds containing halogen-substitutedbenzothiadiazole (BT, benzo[c][1,2,5]thiadiazole), benzooxadizaole (BO,benzo[c][1,2,5]oxadiazole), benzotriazole (B3N,2H-benzo[d][1,2,3]triazole), benzoselenadiazole (BSe,benzo[c][1,2,5]selenadiazole), benzotelluradiazole (BTe,benzo[c][1,2,5]selenadiazole), 2,3-dihydroquinoxaline, and quinoxalinestructures for use in heterojunction devices, such as organic smallmolecule solar cells and transistors. In one embodiment, the presentinvention is directed to non-polymeric electron-donating andelectron-accepting chromophores having a halogen-substitutedbenzothiadiazole (BT, benzo[c][1,2,5]thiadiazole), benzooxadizaole (BO,benzo[c][1,2,5]oxadiazole), 2-substituted benzotriazole (B3N,2H-benzo[d][1,2,3]triazole) core structure. In other embodiments, thepresent invention is directed to optoelectronic devices comprising afirst electrode, a second electrode and an active layer between the thetwo electrodes containing a compound described herein.

Embodiments include electronic or optoelectronic devices usingnon-polymeric compounds, said compound incorporating one or more groupsof Formula A:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. In someembodiments, both X₁ and Y₁ are halogen.

Embodiments include compounds having Formula B:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. In someembodiments, both X₁ and Y₁ are halogen.

H₁ is selected from —B₂, −A₁-B₁, −A₁-B₂, or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. A₁ is independently selectedfrom substituted or unsubstituted aryl group, substituted orunsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₁ is independently selected from a an aryl or heteroaryl groupssubstituted with one, two, or more B₂.

Each B₂ is independently selected from H, a substituent or

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent;

H₂ is selected from —B₂, −A₁-B₁, −A₁-B₂,

where p is 1, 2, or 3. Each X₂ is independently H or halogen and each Y₂is independently H or halogen, where at least one of X₂ and Y₂ ishalogen. In some embodiments, both X₁ and Y₁ are halogen. In someembodiments, both X₂ and Y₂ are halogen. Each J₁ is independentlyselected from a nonentity, substituted or unsubstituted aryl,substituted or unsubstituted heteroaryl groups, or

Q is a bivalent, trivalent, or tetravalent aryl or heteroaryl group or

L₁ is selected from —B₂, −A₁-B₁, −A₁-B₂,

where each A₁ is independently selected from substituted orunsubstituted aryl or heteroaryl groups, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups.

With the proviso that H₁ and H₂ are not both —B₂.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows geometry optimized structure, HOMO-LUMO orbital schemes andenergies of an example compound using Density Functional Theory(B3LYP/6-31G**-Spartan '10, Wavefunction, Inc.)

FIG. 2 shows absorption properties of an example compound in solutionand film.

FIG. 3 is a schematic illustration of an example device according to anembodiment of the invention.

FIG. 4 shows J-V characteristics of an example device according to someembodiments of the invention.

FIG. 5 shows absorption properties of an example compound in chloroformsolution.

FIG. 6 shows absorption properties of an example compound in a film onan ITO substrate, as cast, and after annealing at 125° C.

FIG. 7 shows a DSC curve for an example compound.

DETAILED DESCRIPTION Definitions

The terms “alkyl” used alone or as part of a larger moiety (i.e.“alkoxy,” “hydroxyalkyl,” “alkoxyalkyl,” and “alkoxycarbonyl”) includeboth straight and branched saturated hydrocarbon chains containing oneto sixteen carbon atoms (i.e. 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, or 16 carbon atoms), as well as cyclic structures. Alkyl groupsmay be independently defined between any two endpoints within thisrange, so that a particular alkyl group may have, for example, 1 to 12carbons, 1 to 6 carbons, 1 to 4 carbons, 6-16 carbons, 6-12 carbons, andso forth. Examples of alkyl groups include methyl (Me), ethyl (Et),propyl (Pr) (including n-propyl (^(n)Pr or n-Pr), isopropyl (^(i)Pr ori-Pr) and cyclopropyl (^(c)Pr or c-Pr)), butyl (Bu) (including n-butyl(^(n)Bu or n-Bu), isobutyl (^(i)Bu or i-Bu), tert-butyl (^(t)Bu or t-Bu)and cyclobutyl (^(c)Bu or c-Bu)), pentyl (Pe) (including n-pentyl) andso forth. Alkyl groups also include mixed cyclic and linear alkylgroups, such as cyclopentylmethyl, cyclopentylethyl, cyclohexylmethyl,etc., so long as the total number of carbon atoms is not exceeded. Theterm “alkoxy” refers to an —O-alkyl radical, such as, for example —O-Me,—O-Et, —O—Pr, and so on. The term “hydroxyalkyl” refers to an alkylgroup substituted with one or more hydroxyl, such as, for example,hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1,2-dihydroxyethyl, andso forth. The term “alkylthio” refers to an —S-alkyl group, such as, forexample, example —S-Me, —S-Et, —S—Pr. The term “haloalkyl” means alkyl,substituted with one or more halogen atoms, such as trifluoromethyl,chloromethyl, 2,2,2-trifluoroethyl, 1,1,2,2,2,-petanfluoroethyl, and soon, and includes “fluoroalkyl,” where at least one carbon atom in thealkyl chain is substituted with fluorine, and perfluoro alkyl, where allhydrogen atoms on the alkyl chain are replaced with fluorine. The term“aminoalkyl” means alkyl, substituted with an amine group (NH₂), suchas, for example, aminomethyl, 1-aminoethyl, 2-aminoethyl, 3-aminopropyland so forth. The term “alkoxyalkyl” refers to an alkyl group,substituted with an alkoxy group, such as, for example, methoxymethyl,ethoxymethyl, methoxyethyl, and so forth. As used herein, the term“alkylaminoalkyl” refers to an alkyl group substituted with analkylamine group, such as, for example, N-methylaminomethyl,N,N-dimethylaminomethyl, N,N-methylpentylaminomethyl,2-(N-methylamino)ethyl, 2-(N,N-dimethylamino)ethyl, and so forth.

The term “halogen” or “halo” means F, Cl, Br, or I.

The term “nitro” means (—NO₂).

The term “hydroxy” or “hydroxyl” means —OH.

The term “amine” or “amino” used alone or as part of a larger moietyrefers to unsubstituted (—NH₂). The term “alkylamine” refers tomono-(—NRH) or di-substituted (—NR₂) amine where at least one R group isan alkyl substituent, as defined above. Examples include methylamino(—NHCH₃), dimethylamino (—N(CH₃)₂), The term “arylamine” refers to amono (—NRH) or di-substituted (—NR₂) amine, where at least one R groupis an aryl group as defined below, including, for example, phenylamino,diphenylamino, and so forth. The term “heteroarylamine” refers to a mono(—NRH) or di-substituted (—NR₂) amine, where at least one R group is aheteroaryl group as defined below, including, for example,2-pyridylamino, 3-pyridylamino and so forth. The term “aralkylamine”refers to a mono (—NRH) or di-substituted (—NR₂) amine, where at leastone R group is an aralkyl group, including, for example, benzylamino,phenethylamino, and so forth. The term “heteroaralkylamine” refers to amono (—NRH) or di-substituted (—NR₂) amine, where at least one R groupis a heteroaralkyl group. As used herein, the term “alkylaminoalkyl”refers to an alkyl group substituted with an alkylamine group.Analogously, “arylaminoalkyl” refers to an alkyl group substituted withan arylamine, and so forth, for any substituted amine described herein.

The term “alkenyl” used alone or as part of a larger moiety include bothstraight and branched chains containing at least one double bond and twoto sixteen carbon atoms (i.e. 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13,14, 15, or 16 carbon atoms), as well as cyclic, non-aromatic alkenylgroups such as cyclopropenyl, cyclobutenyl, cyclopentenyl,cyclopentadienyl, cyclohexenyl, cyclohexadienyl, etc. As used herein,alkenyl groups also include mixed cyclic and linear alkyl groups, suchas cyclopentenylmethyl, cyclopentenylethyl, cyclohexenylmethyl, etc., solong as the total number of carbon atoms is not exceeded. When the totalnumber of carbons allows (i.e. more than 4 carbons), an alkenyl groupmay have multiple double bonds, whether conjugated or non-conjugated,but do not include aromatic structures. Examples of alkenyl groupsinclude ethenyl, propenyl, butenyl, butadienyl, isoprenyl,dimethylallyl, geranyl and so forth.

The term “aryl” used alone or as part of a larger moiety, refers tomono-, bi-, tri-, or larger aromatic hydrocarbon ring systems havingfive to thirty members. Aryl groups may be independently defined betweenany two endpoints within this range, so that a particular aryl group mayhave, for example, 5 to 24 members, 6 to 24 members, 6 to 14 members, 10to 30 members, and so forth. The term “aryl” may be used interchangeablywith the term “aryl ring”. “Aryl” also includes fused polycyclicaromatic ring systems in which an aromatic ring is fused to one or morerings. Examples include 1-naphthyl, 2-naphthyl, 1-anthracyl and2-anthracyl. Also included within the scope of the term “aryl”, as it isused herein, is a group in which an aromatic ring is fused to one ormore non-aromatic rings, such as in an indanyl, phenanthridinyl, ortetrahydronaphthyl, and including spiro compounds, such asspirobi[fluorene], where the radical or point of attachment is on thearomatic ring. The term “aralkyl” refers to an alkyl substituentsubstituted by an aryl group. The term “aryloxy” refers to an —O-arylgroup, such as, for example phenoxy, 4-chlorophenoxy and so forth. Theterm “arylthio” refers to an —S-aryl group such as, for examplephenylthio, 4-chlorophenylthio, and so forth. The term “aryl” used aloneor as part of a larger moiety also refers to aryl rings that aresubstituted such as, for example, 4-chlorophenyl, 3,4-dibromophenyl andso forth. An aryl group may have more than one substituent, up to thetotal number of free substitution positions. For example, an aryl groupmay have 1, 2, 3, 4, 5 or more substituents. The substituents may thesame or different. Substituents on an aryl group include hydrogen,halogen, alkyl, alkenyl, nitro, hydroxyl, amino, alkylamino, alkoxy, andalkylthio, acyl, O-acyl, N-acyl, S-acyl as defined herein.

The term “heteroaryl”, used alone or as part of a larger moiety, refersto heteroaromatic ring groups having five to thirty members, in whichone or more ring carbons (1 to 6, 1 to 4, 1 to 3, 1 to 2, or 1), areeach replaced by a heteroatom such as N, O, S, or Si. Heteroaryl groupsmay be independently defined between any two endpoints within thisrange, so that a particular heteroaryl group may have, for example, 5 to24 members, 6 to 24 members, 6 to 14 members, 10 to 30 members, and soforth. Examples of heteroaryl rings include 2-furanyl, 3-furanyl,N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl,4-isoxazolyl, 5-isoxazolyl, 2-oxadiazolyl, 5-oxadiazolyl, 2-oxazolyl,4-oxazolyl, 5-oxazolyl, 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl,3-pyrazolyl, 4-pyrazolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidyl,4-pyrimidyl, 5-pyrimidyl, 3-pyridazinyl, 2-thiazolyl, 4-thiazolyl,5-thiazolyl, 5-tetrazolyl, 2-triazolyl, 5-triazolyl, 2-thienyl,3-thienyl, carbazolyl, benzimidazolyl, benzothienyl, benzofuranyl,indolyl, quinolinyl, benzotriazolyl, benzothiazolyl, benzooxazolyl,benzimidazolyl, isoquinolinyl, indazolyl, isoindolyl, acridinyl,benzoisoxazolyl. Other specific examples include thiophene, pyrrole,furan, phosphole, benzodithiophene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b]-dithiophene where R and R′═C₁-C₃₀ alkylor C₆-C₃₀ aryl. Also included within the scope of the term “heteroaryl”,as it is used herein, is a group in which a heteroaromatic ring is fusedto one or more aromatic or nonaromatic rings, including spiro compounds,where the radical or point of attachment is on the heteroaromatic ring.Examples include tetrahydroquinolinyl, tetrahydroisoquinolinyl,pyrido[3,4-d]pyrimidinyl, spirobi[dibenzo[b,c]silole],spirobi[cyclopenta[1,2-b:5,4-b′]dithiophene], orspirobi[silolo[3,2-b:4,5-b′]dithiophene]. The term “heteroaryl” may beused interchangeably with the term “heteroaryl ring” or the term“heteroaromatic.” The term “heteroaralkyl” refers to an alkyl groupsubstituted by a heteroaryl, such as, for example, 2-pyridylmethyl,3-pyridylmethyl, 1-imidazolomethyl, 2-imidazolomethyl and so forth. Theterm “heteroaryloxy” refers to an —O-heteroaryl group. The term“heteroarylthio” refers to an —S-aryl group. A heteroaryl group may havemore than one substituent, up to the total number of free substitutionpositions. For example, a heteroaryl group may have 1, 2, 3, 4, or 5 substituents. The substituents may the same or different. Substituents on aheteroaryl group include hydrogen, halogen, alkyl, alkenyl, nitro,hydroxyl, amino, alkylamino, alkoxy, and alkylthio, acyl, O-acyl,N-acyl, S-acyl as defined herein.

The term “acyl” refers to an “—C(O)-alkyl,” “C(O)-aryl,” or“C(O)-heteroaryl” group. The term “O-acyl” refers to an “—O—C(O)-alkyl,”“—O—C(O)-aryl,” or “—O—C(O)— heteroaryl” group. The term “N-acyl” refersto an “—NR—C(O)-alkyl,” “—NR—C(O)-aryl,” or “—NR—C(O)-heteroaryl” whereR is an alkyl, hydroxyl, or alkoxy group. The term “S-acyl” refers to“—S—C(O)-alkyl,” “—S—C(O)-aryl,” or “—S—C(O)-heteroaryl.” The term“N—O-acyl” refers to an “N—O—C(O)-alkyl,” “N—O—C(O)-aryl,” or“N—O—C(O)-heteroaryl” group.

As used herein, a “substituted” structure refers to a chemical structurewhere a hydrogen atom has been replaced by a substituent. A“substituent” is a chemical structure that replaces a hydrogen atom onthe substituted structure, and may be, independently, any chemicalmoiety defined previously. When present, multiple substituents may bethe same or different. The term “substituent” does not imply that thesubstituent is smaller than the substituted structure. In someembodiments, a “substituent” may be halogen, F, NO₂, CN, acyl, O-acyl,S-acyl, N-acyl, alkyl, haloalkyl, substituted or unsubstituted aryl,substituted or unsubstituted heteroaryl, alkenyl, alkoxy, alkylthio,alkylamine, arylamine, or hydroxy.

“Polymer” or “polymeric molecule” is defined herein as a structurecontaining at least eight repeating units. A “non-polymeric” molecule isa molecule containing seven or fewer repeating units. Thus, monomers,dimers, trimers, tetramers, pentamers, hexamers, and heptamers arenon-polymeric molecules for the purposes of this disclosure.Interruption of a repeating unit “resets” the count of subunits for thepurposes of this disclosure; thus, for example, for a molecule such asFormula 6:

when n is 5, the molecule is considered to have two separatefive-subunit pieces, that is, it is comprised of two pentamers ofthiophene, and is not considered a decamer or 10-subunit polymer ofthiophene.

Non-polymeric molecules have a discrete molecular weight, whilepolymeric molecules usually have a distribution of molecular weights dueto varying numbers of monomers that are incorporated into the growingchain during polymerization. Thus, in one embodiment, a preparation of anon-polymer molecule will be characterized by a single molecular weight(where the molecular weight is averaged only over isotopic variation dueto differing isotopes such as hydrogen, deuterium, carbon-12, carbon-13,etc.). In contrast, preparations of a polymeric molecule will have adistribution of molecular weights due to varying numbers of monomers inthe final polymer, where the molecular weight is an average over eachindividual polymeric species present in a given preparation (measured ineither number-average molecular weight or weight-average molecularweight).

In some embodiments, compositions of the non-polymeric moleculesdescribed herein are not part of a mixture of oligomers or polymers. Inother words, in some embodiments, compositions comprising thenon-polymer molecules described herein will not contain oligomers orpolymers having a repeating structure in common with the non-polymericmolecules described herein. In some embodiments, the non-polymermolecule is substanially pure, i.e. the molecules described herein maybe greater than 90% pure, greater than 95% pure, or greater than 98%pure.

Small Molecules

Some embodiments of the current invention provide several advantages forpreparation of optoelectronic devices. The organic materials describedare non-polymeric allowing for synthesis and purification to be morerepeatable than organic polymers. Unlike polymers, the organic materialsdescribed are discrete mono-disperse small molecules which allows fortheir exact structure to be known and reproduced.

Organic compounds described herein may have favorable frontier molecularorbital levels (HOMO and LUMO) to accept and transport holes andelectrons. The organic small molecule compounds described also havefavorable frontier molecular orbital levels (HOMO and LUMO) for use aselectron donating materials in organic solar cell devices withfullerene, methanofullerene, rylene diimides or related π-conjugatedorganic electron acceptors. In addition, the organic small moleculechromophores described have favorable frontier molecular orbital levels(HOMO and LUMO) for use as electron accepting materials in organic solarcell devices with thiophene or phenyl based π-conjugated organicelectron donors.

The optical properties of the compounds are also very good. The organicsmall molecule chromophores described have broad absorption spectra thatabsorb ultraviolet, visible, and near infrared radiation. The absorptionspectra of the organic small molecule chromophores described have afavorable spectral overlap with the terrestrial solar spectrum, makingthem excellent light harvesting materials for organic solar cells.

The compounds are also readily handled in solution, as the organic smallmolecules described retain good solubility in many common organicsolvents. This allows solution processing during the preparation of theoptoelectronic devices.

While solution processing may be advantageous for its ease of handlingand low cost, vapor deposition can also be used, or mixtures of saidmolecules with other components, which are suitable for use in such amethod (e.g., vacuum deposition, physical vapor deposition, chemicalvapor deposition).

Embodiments of the invention include compounds having Formula B:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; R₃ is H or a substituent. X₁ is H or halogen and Y₁ is H orhalogen, where at least one of X₁ and Y₁ is halogen. In someembodiments, both X₁ and Y₁ are halogen.

H₁ is selected from —B₂, −A₁-B₁, −A₁-B₂, or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. A₁ is independently selectedfrom substituted or unsubstituted aryl group, substituted orunsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group. Each B₁ is independentlyselected from a an aryl or heteroaryl groups substituted with one, two,or more B₂. Each B₂ is independently selected from H, a substituent or

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent.

H₂ is selected from —B₂, −A₁-B₁, −A₁-B₂,

where p is 1, 2, or 3, n is an integer between 0 and 5, inclusive, and mis an integer between 0 and 5, inclusive, and 1≤m+n≤5. Each X₂ isindependently H or halogen and each Y₂ is independently H or halogen,where at least one of X₂ and Y₂ is halogen. Each J₁ is independentlyselected from a nonentity, substituted or unsubstituted aryl,substituted or unsubstituted heteroaryl groups, or

Q is a bivalent, trivalent, or tetravalent aryl or heteroaryl group or

L₁ is selected from —B₂, −A₁-B₁, −A₁-B₂,

where each A₁ is independently selected from substituted orunsubstituted aryl group, substituted or unsubstituted heteroaryl groupexcept thiophene,

orwhere A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

In Formula B, H₁ and H₂ are not both —B₂.

In some compounds according to Formula B, M is S. In some compoundsaccording to Formula B, all X_(n) and Y_(n) substituents are halogen. Inother words, X₁, Y₁, X₂, Y₂ are all halogen. In some compounds accordingto formula B, all X_(n) and Y_(n) substituents are fluorine.

In some compounds according to Formula B, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula B, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula B, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

In some compounds according to Formula B, H₂ is

where p is 1, and H₁ and L₁ are the same.

In some compounds according to Formula B, H₁ is

In some compounds according to formula B, B₁ is substituted by one B₂.

In some compounds according to formula B, each J₁ is a nonentity.

In some compounds according to formula B, H₂ is

where p is 1, both J₁ are both nonentities, and L₁ and H₁ are the sameand are both

where B₁ is substituted by one B₂.

Some compounds according to formula B have Formula II, shown below:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent; Each n is an integer between0 and 5, inclusive, and each m is an integer between 0 and 5, inclusive,and 1≤m+n≤5. X₁ is H or halogen and Y₁ is H or halogen, where at leastone of X₁ and Y₁ is halogen. X₂ is H or halogen and each Y₂ is H orhalogen, where at least one of X₂ and Y₂ is halogen. Q is a bivalentaryl or heteroaryl group. Each B₁ is independently selected from a anaryl or heteroaryl groups. Each B₂ is independently selected from H or asubstituent; where R₁, R₂, R₃, and R₄ are each independently H or asubstituent.

In some compounds according to Formula II, B₁ is a substituted orunsubstituted thiophene.

In some compounds according to Formula II, Q may be thiophene, pyrrole,furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl.

In some compounds according to formula II, B₁ may be, independently,thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some compounds according to Formula II, Q is3,3′-RR′silylene-2,2′-bithiophene and R and R′ are both C₁-C₃₀ alkyl.

In some compounds according to Formula II, Q is

In some compounds according to Formula II, n+m=1.

In some compounds according to Formula II, B₂ is alkyl.

In some compounds according to Formula II, Q is3,3′-RR′silylene-2,2′-bithiophene and R and R′ are both C₁-C₃₀ alkyl, B₁is thiophene, n+m=1, and B₂ is alkyl.

For example, the compound according to Formula II may have the structure

In some compounds according to Formula II, M is S. In some compoundsaccording to Formula II, all X_(n) and Y_(n) substituents are halogen.In other words, X₁, Y₁, X₂, Y₂ are all halogen. In some compoundsaccording to formula II, all X_(n) and Y_(n) substituents are fluorine.

In some compounds according to Formula B, H₂ is

where p is 1, both J₁ are both nonentities, and L₁ and H₁ are the sameand are both —B₂ or −A₁—B₂.

Some compounds according to Formula B have Formula I:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and each Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. Q is a bivalent aryl or heteroaryl group.

Each L₂ is independently —B₂ or −A₁-B₂. Each A₁ is independentlyselected from substituted or unsubstituted aryl group, substituted orunsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group;

Each B₂ is independently selected from H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5, and where R₁, R₂, R₃, R₄ and R₅are each independently H or a substituent.

In some compounds according to Formula I, Q may be substituted orunsubstituted thiophene, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene where R and R′═C₁-C₃₀ alkylor C₆-C₃₀ aryl.

In some compounds according to Formula I, each L₂ is −A₁-B₂.

In some compounds according to Formula I, and A₁ is independentlysubstituted or unsubstituted thiophene, pyrrole, furan, phenyl,phosphole, benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In some compounds according to Formula I each L₂ is B₂.

In some compounds according to Formula I B₂ is

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5; and where R₁, R₂, R₃, R₄ and R₅are each independently H or a substituent.

In some compounds according to Formula B, H₁ and H₂ are the same.

In some compounds according to Formula I, M is S. In some compoundsaccording to Formula I, all X_(n) and Y_(n) substituents are halogen. Inother words, X₁, Y₁, X₂, Y₂ are all halogen. In some compounds accordingto Formula I, all X_(n) and Y_(n) substituents are fluorine.

In some compounds according to Formula I, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula I, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula I, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds according to Formula B have Formula III:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen.

H₃ is selected from −A₁-B₁, −A₁-B₂, or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5.

Each A₁ is independently selected from substituted or unsubstituted arylgroup, substituted or unsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₁ is independently selected from a an aryl or heteroaryl groupsoptionally substituted with one, two, or more B₂. Each B₂ isindependently selected from a substituent or

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent.

In some compounds according to formula III, H₃ is −A₁-B₂, or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. Each B₁ is independentlyselected from a an aryl or heteroaryl groups optionally substituted withone, two, or more B₂. Each B₂ is independently selected from asubstituent or

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent.

In some compounds according to Formula III, A₁ is a DONOR, definedbelow.

In some compounds according to Formula III, H₃ is −A₁-B₂, or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 and A₁ is a DONOR, definedbelow. Each B 1 is independently selected from a an aryl or heteroarylgroups optionally substituted with one, two, or more B₂. Each B₂ isindependently selected from H, a substituent or

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent.

In some compounds according to Formula III, B₂ is H or a substituent.

In some compounds according to Formula III, B₂ is

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent.

In some compounds according to Formula III, —B₁ is

where J is selected from CH and N, and X is S, O, or NH when X is CH;and X is S when J is N.

In some compounds according to Formula III, —B₁ is R₆ is selected fromaryl, perfluoroaryl, or C₆-C₃₀ aryl optionally perfluorinated.

In some compounds according to Formula III, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, and Y₁ are all halogen. Insome compounds according to Formula III, all X_(n) and Y_(n)substituents are fluorine.

In some compounds according to Formula III, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula III, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula III, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds according to Formula III have Formulas 6, 7, or 8

where n is an integer from 0 to 5 inclusive; m is an integer from 0 to 5inclusive. M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. R₇ is selectedfrom H or a substituent. J is selected from CH and N. X is S, O, or NHwhen X is CH; and X is S when J is N. R₆ is selected from aryl,perfluoroaryl, or C₆-C₃₀ aryl optionally perfluorinated or optionallysubstituted with one or more C₁-C₁₆ alkyl groups.

In some compounds according to Formulas 6, 7, or 8, all X_(n) and Y_(n)substituents are halogen. In other words, X₁ and Y₁ are all halogen. Insome compounds according to Formulas 6, 7, or 8, all X_(n) and Y_(n)substituents are fluorine

In some compounds according to Formulas 6, 7, or 8, M is —N(R₁)— whereR₁ is H, alkyl, or haloalkyl. In some compounds according to Formulas 6,7, or 8, M is —N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In somecompounds according to Formulas 6, 7, or 8, M is —N(R₁)— where R₁ hasthe formula —C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, andy is at least 1.

In some compounds according to Formula B, H₂ is

where p is 2.

In some compounds according to formula B, H₂ is

where p is 2, and H₁ and each L₁ are the same.

In some compounds according to formula B, H₂ is

where p is 2, and H₁ and each L₁ are the same and are —B₂ or −A₁-B₂.

Some compounds according to Formula B have Formula IV-V:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and each Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. X₃ is H or halogen and each Y₃ is H or halogen, where at leastone of X₃ and Y₃ is halogen. Q is a trivalent aryl or heteroaryl group.

Each E₁ is independently either nonentity, substituted or unsubstitutedaryl, substituted or unsubstituted heteroaryl groups, or

Each L₃ is, independently, —B₂ or −A₁-B₂.

Each A₁ is independently selected from substituted or unsubstituted arylgroup, substituted or unsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₂ is independently selected from, H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. R₁, R₂, R₃, R₄ and R₅ are eachindependently H or a substituent.

In some compounds according to Formula IV-V, E₁ is a nonentity.

In some compounds according to Formula IV-V, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, Y₂, X₃, and Y₃ areall halogen. In some compounds according to Formula IV-V, all X_(n) andY_(n) substituents are fluorine.

In some compounds according to Formula IV-V, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula IV-V, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula IV-V, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds according to Formula IV-V have formula IVa

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and each Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. X₃ is H or halogen and each Y₃ is H or halogen, where at leastone of X₃ and Y₃ is halogen. Q is a trivalent aryl or heteroaryl group.

Each L₃ is, independently, —B₂ or −A₁-B₂.

Each A₁ is independently selected from substituted or unsubstituted arylgroup, substituted or unsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₂ is independently selected from, H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. And where R₁, R₂, R₃, R₄ and R₅are each independently H or a substituent.

In some compounds according to Formula IVa, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, Y₂, X₃, and Y₃ areall halogen. In some compounds according to Formula IVa, all X_(n) andY_(n) substituents are fluorine.

In some compounds according to Formula IVa, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula IVa, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula IVa, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

In some compounds according to Formula IV-V, each E₁ is independently, asubstituted or unsubstituted aryl, a substituted or unsubstitutedheteroaryl group, or

Some compounds according to Formula IV-V have Formula Va:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁is Hor halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and each Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. X₃ is H or halogen and each Y₃ is H or halogen, where at leastone of X₃ and Y₃ is halogen. Q is a trivalent aryl or heteroaryl group.

Each E₁ is independently a substituted or unsubstituted aryl, asubstituted or unsubstituted heteroaryl groups, or

Each L₃ is, independently, —B₂ or −A₁-B₂.

Each A₁ is independently selected from substituted or unsubstituted arylgroup, substituted or unsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₂ is independently selected from, H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. R₁, R₂, R₃, R₄ and R₅ are eachindependently H or a substituent.

In some compounds according to Formula B, H₂ is

where p is 3.

In some compounds according to formula B, H₂ is

where p is 3, and H₁ and each L₁ are the same.

In some compounds according to formula B, H₂ is

where p is 3, and H₁ and each L₁ are the same and are —B₂ or −A₁-B₂.

In some compounds according to Formula Va, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, Y₂, X₃, and Y₃ areall halogen. In some compounds according to Formula Va, all X_(n) andY_(n) substituents are fluorine.

In some compounds according to Formula Va, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula Va, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula Va, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds according to Formula B have Formula VI-VII:

where the moiety

is a tetravalent aryl or heteroaryl group selected from

-   (2,2′,7,7′-yl-9,9′-spirobi[fluorene]),

-   (3,3′,7,7′-yl-5,5′-spirobi[dibenzo[b,d]silole]),

-   (2,2′,6,6′-yl-4,4″-spirobi[cyclopenta[1,2-b:5,4-b′]dithiophene]), or

-   (2,2′,6,6′-yl-4,4′-spirobi[silolo[3,2-b:4,5-b′]dithiophene]);    where M is selected from sulfur (S), oxygen (O), selenium (Se),    tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—,    —S(═O)—, —C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent;    R₂ is H or a substituent; and R₃ is H or a substituent. X₁ is H or    halogen and Y₁ is H or halogen, where at least one of X₁ and Y₁ is    halogen. X₂ is H or halogen and Y₂ is H or halogen, where at least    one of X₂ and Y₂ is halogen. X₃ is H or halogen and Y₃ is H or    halogen, where at least one of X₃ and Y₃ is halogen. X₄ is H or    halogen and Y₄ is H or halogen, where at least one of X₄ and Y₄ is    halogen

Each F₁ is independently either nonentity, substituted or unsubstitutedaryl, substituted or unsubstituted heteroaryl groups, or

Each L₄ is, independently, —B₂ or −A₁-B₂.

Each A₁ is independently selected from substituted or unsubstituted arylgroup, substituted or unsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₂ is independently selected from, H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. And where R₁, R₂, R₃, R₄ and R₅are each independently H or a substituent.

In some compounds according to Formula VI-VII, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, Y₂, X₃, Y₃, X₄,and Y₄ are all halogen. In some compounds according to Formula VI-VII,all X_(n) and Y_(n) substituents are fluorine.

In some compounds according to Formula VI-VII, M is —N(R₁)— where R₁ isH, alkyl, or haloalkyl. In some compounds according to Formula VI-VII, Mis —N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula VI-VII, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds according to Formula VI-VII have Formula VIa:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. X₃ is H or halogen and Y₃ is H or halogen, where at least oneof X₃ and Y₃ is halogen. X₄ is H or halogen and Y₄ is H or halogen,where at least one of X₄ and Y₄ is halogen

Each F₁ is independently either nonentity, substituted or unsubstitutedaryl, substituted or unsubstituted heteroaryl groups, or

Each L₄ is, independently, —B₂ or −A₁—B₂.

Each A₁ is independently selected from substituted or unsubstituted arylgroup, substituted or unsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₂ is independently selected from, H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. And where R₁, R₂, R₃, R₄ and R₅are each independently H or a substituent.

In some compounds according to Formula VIa, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, Y₂, X₃, Y₃, X₄,and Y₄ are all halogen. In some compounds according to Formula VIa, allX_(n) and Y_(n) substituents are fluorine.

In some compounds according to Formula VIa, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula VIa, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula VIa, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds according to Formula VI-VII have Formula VIIa:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. X₃ is H or halogen and Y₃ is H or halogen, where at least oneof X₃ and Y₃ is halogen. X₄ is H or halogen and Y₄ is H or halogen,where at least one of X₄ and Y₄ is halogen

Each F₁ is independently either nonentity, substituted or unsubstitutedaryl, substituted or unsubstituted heteroaryl groups, or

Each L₄ is, independently, —B₂ or −A₁—B₂.

Each A₁ is independently selected from substituted or unsubstituted arylgroup, substituted or unsubstituted heteroaryl group except thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group.

Each B₂ is independently selected from, H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. R₁, R₂, R₃, R₄ and R₅ are eachindependently H or a substituent.

In some compounds according to Formula VIIa, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, Y₂, X₃, Y₃, X₄,and Y₄ are all halogen. In some compounds according to Formula VIIa, allX_(n) and Y_(n) substituents are fluorine.

In some compounds according to Formula VIIa, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula VIIa, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula VIIa, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

In some compounds according to Formula B, Q is a DONOR.

In some compounds according to Formula B, H₂ is

where p is 1, and H₁ and L₁ are the same, and both H₁ and L₁ are —B₂,where B₂ is independently selected from, H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. And where R₁, R₂, R₃, R₄ and R₅are each independently H or a substituent.

In some compounds of formula B, Q is a DONOR, H₂ is

where p is 1, each J₁ is a nonentity, and H₁ and L₁ are the same, andboth H₁ and L₁ are —B₂, where B₂ is independently selected from, H, asubstituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5. R₁, R₂, R₃, R₄ and R₅ are eachindependently H or a substituent.

Some compounds of Formula B have Formula 1:

where n is an integer from 0 to 5 inclusive, M is selected from sulfur(S), oxygen (O), selenium (Se), tellurium (Te), —N(R₁)—,—C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—, —C(═O)—, —C(═S)—, or—C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or a substituent; and R₃is H or a substituent. X₁ is H or halogen and Y₁ is H or halogen, whereat least one of X₁ and Y₁ is halogen. X₂ is H or halogen and each Y₂ isH or halogen, where at least one of X₂ and Y₂ is halogen. R₇ is selectedfrom H or a substituent.

In some compounds of formula B, H₂ is

where p is 1, H₁ and L₁ are the same, and both H₁ and L₁ are

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 where each B₁ is independentlyselected from an aryl or heteroaryl groups substituted with one, two, ormore B₂. Each B₂ is independently selected from H, a substituent or

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent.

In some compounds of formula B, H₁ and L₁ may be

In some compounds of formula B, B₁ is substituted by two B₂.

In some compounds of formula B, H₂ is

where p is 1, each J₁ is a nonentity, H₁ and L₁ are the same, and bothH₁ and L₁ are

and each B₁ is an aryl or heteroaryl group substituted with two B₂,where each B₂ is independently selected from H, a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5 and where R₁, R₂, R₃, R₄ and R₅ are each independently Hor a substituent.

In some compounds according to Formula 1, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, and Y₂ are allhalogen. In some compounds according to Formula 1, all X_(n) and Y_(n)substituents are fluorine.

In some compounds according to Formula 1, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula 1, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula 1, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds of formula B have formula 2:

where n is an integer from 0 to 5 inclusive, M is selected from sulfur(S), oxygen (O), selenium (Se), tellurium (Te), —N(R₁)—,—C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—, —C(═O)—, —C(═S)—, or—C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or a substituent; and R₃is H or a substituent. X₁ is H or halogen and Y₁ is H or halogen, whereat least one of X₁ and Y₁ is halogen. X₂ is H or halogen and each Y₂ isH or halogen, where at least one of X₂ and Y₂ is halogen. R₇ is selectedfrom H or a substituent.

In some compounds of formula B, H₂ is

where p is 1, H₁ and L₁ are the same, and both H₁ and L₁ are −A₁-B₂ or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 where each B₁ is independentlyselected from an aryl or heteroaryl groups substituted with one, two, ormore B₂. Each B₂ is independently selected from H, a substituent or

where R₁, R₂, R₃, R₄ and R₅ are each independently H or a substituent.

In some compounds of formula B, B₂ is H or a substituent.

In some compounds of formula B, H₂ is

where p is 1, H₁ and L₁ are the same, and both H₁ and L₁ are −A₁-B₂ or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 where each B₁ is independentlyselected from an aryl or heteroaryl groups substituted with one, two, ormore B₂. Each B₂ is independently selected from H or a substituent.

In some compounds of formula B, −A₁-B₂ is

where J is selected from CH and N, and X is S, O, or NH when X is CH;and X is S when J is N.

In some compounds of formula B, —B₁ is

where J is selected from CH and N, and X is S, O, or NH when X is CH;and X is S when J is N.

In some compounds according to Formula 2, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, and Y₂ are allhalogen. In some compounds according to Formula 2, all X_(n) and Y_(n)substituents are fluorine.

In some compounds according to Formula 2, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula 2, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula 2, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds of formula B have formula 3:

where n is an integer from 0 to 5 inclusive, J is selected from CH and Nand X is S, O, or NH when X is CH; and X is S when J is N. M is selectedfrom sulfur (S), oxygen (O), selenium (Se), tellurium (Te), —N(R₁)—,—C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—, —C(═O)—, —C(═S)—, or—C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or a substituent; and R₃is H or a substituent. X₁ is H or halogen and Y₁ is H or halogen, whereat least one of X₁ and Y₁ is halogen. X₂ is H or halogen and each Y₂ isH or halogen, where at least one of X₂ and Y₂ is halogen.

In some compounds of formula B, B₁ is substituted by one B₂.

In some compounds of formula B, B₂ is diarylamine.

In some compounds of formula B, B₁ is phenyl.

In some compounds of formula B, A₁ is phenyl

In some compounds of formula B, H₂ is

where p is 1, each J₁ is a nonentity, H₁ and L₁ are the same, and bothH₁ and L₁ are −A₁-B₂ where A₁ is phenyl or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 where each B₁ is phenylsubstituted with one B₂. Each B₂ is independently selected from H ordiarylamine.

In some compounds according to Formula 3, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, and Y₂ are allhalogen. In some compounds according to Formula 3, all X_(n) and Y_(n)substituents are fluorine.

In some compounds according to Formula 3, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula 3, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula 3, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds of formula B have formula 4:

where n is an integer from 0 to 5 inclusive, J is selected from CH and Nand X is S, O, or NH when X is CH; and X is S when J is N. M is selectedfrom sulfur (S), oxygen (O), selenium (Se), tellurium (Te), —N(R₁)—,—C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—, —C(═O)—, —C(═S)—, or—C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or a substituent; and R₃is H or a substituent. X₁ is H or halogen and Y₁ is H or halogen, whereat least one of X₁ and Y₁ is halogen. X₂ is H or halogen and each Y₂ isH or halogen, where at least one of X₂ and Y₂ is halogen. R₈ is C₆-C₃₀aryl optionally substituted with one or more C₁-C₁₆ alkyl groups.

In some compounds of formula B, H₂ is

where p is 1, H₁ and L₁ are the same, and both H₁ and L₁ are both −A₁-B₁where each A₁ is independently selected from substituted orunsubstituted aryl group, substituted or unsubstituted heteroaryl groupexcept thiophene,

where A₂ is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group. Each B₁ is independentlyselected from a an aryl or heteroaryl groups optionally substituted withone, two, or more B₂. Each B₂ is independently selected from asubstituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 and R₁, R₂, R₃, R₄ and R₅ areeach independently H or a substituent.

In some compounds of formula B, A₁ is a DONOR.

In some compounds of formula B, H₂ is

where p is 1, H₁ and L₁ are the same, and both H₁ and L₁ are both −A₁-B₁where each A₁ is a DONOR. Each B₁ is independently selected from a anaryl or heteroaryl groups optionally substituted with one, two, or moreB₂. Each B₂ is independently selected from a substituent or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 and R₁, R₂, R₃, R₄ and R₅ areeach independently H or a substituent.

In some compounds of formula B, H₂ is

where p is 1, Q is a DONOR, each J₁ is a nonentity, H₁ and L₁ are thesame, and both H₁ and L₁ are −A₁-B₁ where each A₁ is a DONOR. Each B₁ isphenyl substituted with one, two, or more B₂, and each B₂ isindependently selected from a H or diarylamine.

In some compounds according to Formula 4, all X_(n) and IT, substituentsare halogen. In other words, X₁, Y₁, X₂, and Y₂ are all halogen. In somecompounds according to Formula 4, all X_(n) and Y_(n) substituents arefluorine.

In some compounds according to Formula 4, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula 4, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula 4, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds of formula B have formula 5:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and each Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. R₈ is C₆-C₃₀ aryl optionally substituted with one or moreC₁-C₁₆ alkyl groups.

In some compounds according to Formula B, H₂ is

where p is 2.

In some compounds according to formula B, H₂ is

where p is 2, and H₁ and each L₁ are the same.

In some compounds according to formula B, H₂ is

where p is 3, and H₁ and each L₁ are the same and are −A₁-B₂.

In some compounds according to formula B, J₁ is

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 and R₁, R₂, R₃, and R₄ are eachindependently H.

In some compounds according to formula B, Q is trivalent.

In some compounds according to formula B, Q is a trivalent aryl orheteroaryl group selected from

In some compounds according to formula B, H₂ is

where p is 3, and H₁ and each L₁ are the same and are −A₁-B₂, where A₁is a DONOR, and B₁ is H or a substituent, and each J₁ is a nonentity or

where n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 and R₁, R₂, R₃, and R₄ are eachindependently H.

In some compounds according to Formula 5, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, and Y₂ are allhalogen. In some compounds according to Formula 5, all X_(n) and Y_(n)substituents are fluorine.

In some compounds according to Formula 5, M is —N(R₁)— where R₁ is H,alkyl, or haloalkyl. In some compounds according to Formula 5, M is—N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formula 5, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Some compounds according to formula B have formula 9 or 10:

Where n is an integer from 0 to 5 inclusive; m is an integer from 0 to 5inclusive. M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and each Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. X₃ is H or halogen and each Y₃ is H or halogen, where at leastone of X₃ and Y₃ is halogen.

In some compounds according to Formulas 9 or 10, all X_(n) and Y_(n)substituents are halogen. In other words, X₁, Y₁, X₂, Y₂, X₃, and Y₃ areall halogen. In some compounds according to Formulas 9 or 10, all X_(n)and Y_(n) substituents are fluorine.

In some compounds according to Formulas 9 or 10, M is —N(R₁)— where R₁is H, alkyl, or haloalkyl. In some compounds according to Formula 1, Mis —N(R₁)— where R₁ is fluoroalkyl or perfluoroalkyl. In some compoundsaccording to Formulas 9 or 10, M is —N(R₁)— where R₁ has the formula—C_(n)(H_(x))(F_(y)), where n is from 1 to 12, x+y=2n+1, and y is atleast 1.

Compounds according to Formula B may have, for example, Formula 1,Formula 2, Formula 3, Formula 4, Formula 5, Formula 6, Formula 7,Formula 8, Formula 9 or Formula* 10 as defined herein. In Formulas1-2-3-4-5, each DONOR moiety may be the same or different. In Formulas6-7-8, each DONOR moiety may be the same or different. In Formulas 9-10,each DONOR moiety may be the same or different.

where n is an integer from 0 to 5 inclusive; m is an integer from 0 to 5inclusive.

M is selected from sulfur (S), oxygen (O), selenium (Se), tellurium(Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—, —C(═O)—,—C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. X₂ is H orhalogen and each Y₂ is H or halogen, where at least one of X₂ and Y₂ ishalogen. X₃ is H or halogen and each Y₃ is H or halogen, where at leastone of X₃ and Y₃ is halogen. R₇ is selected from H or a substituent. Jis selected from CH and N. X is S, O, or NH when X is CH; and X is Swhen J is N. R₈ is C₆-C₃₀ aryl optionally substituted with one or moreC₁-C₁₆ alkyl groups. R₆ is selected from aryl, perfluoroaryl, or C₆-C₃₀aryl optionally perfluorinated or optionally substituted with one ormore C₁-C₁₆ alkyl groups.

As used throughout this application, DONOR is a heteroaromatic group,which may be, for example,

where X is C or Si. A is N or P. R₁₁ is selected from C₁-C₁₆ alkyl. R₁₂is selected from C₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ arylsubstituted with one or more substituent. R₁₃ is C₁-C₁₆ alkyl or C₆-C₂₀aryl. R₁₄ is selected from C₁-C₁₆ alkyl, —O—C₁-C₁₆ alkyl,—C(═O)—O—C₁-C₁₆ alkyl, or —O—C(═O)—C₁-C₁₆ alkyl. R₁₅ is selected fromC₁-C₁₆ alkyl, C₆-C₂₀ unsubstituted aryl, or C₆-C₂₀ aryl substituted withone or more substituent.

In any compound described herein, a substituent may be, for example,independently halogen, F, NO₂, CN, acyl, O-acyl, S-acyl, N-acyl, alkyl,haloalkyl, substituted or unsubstituted aryl, substituted orunsubstituted heteroaryl, alkenyl, alkoxy, alkylthio, alkylamine,arylamine, or hydroxy. As such, in any compound described herein, unlessotherwise specified, B₂, R₁, R₂, R₃, R₄, or R₅ may be, independently,halogen, F, NO₂, CN, acyl, O-acyl, S-acyl, N-acyl, alkyl, haloalkyl,substituted or unsubstituted aryl, substituted or unsubstitutedheteroaryl, alkenyl, alkoxy, alkylthio, alkylamine, arylamine, orhydroxy.

In any compound described herein, at least one of R₁, R₂, R₃, or R₄ maybe alkyl.

In any compound described herein, M may be S. In any compound describedherein, M may be Se. In any compound described herein, M may be O.

In any compound described herein, all X_(n) and Y_(n) substituents maybe halogen. In other words, every X and Y substituent, regardless of thesubscript may be halogen.

In some compounds described herein, all X_(n) and Y_(n) substituents maybe fluorine.

In any compound described herein, unless otherwise specified, A₁ (whenpresent) may be, for example, substituted or unsubstituted aryl orheteroaryl groups except thiophene, such as C₆-C₃₀ substituted orunsubstituted aryl or heteroaryl groups, C₆-C₂₀ substituted orunsubstituted aryl or heteroaryl groups, and C₆-C₁₀ substituted orunsubstituted aryl or heteroaryl groups. Examples of such groupsinclude, but are not limited to, pyrrole, furan, phenyl, phosphole,benzodithiophene, spirofluorene, spirothiophene, bithiophene,terthiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole, 3,3′-RR′silylene-2,2′-bithiophene, 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene,where R and R′═C₁-C₃₀ alkyl or C₆-C₃₀ aryl;

In any compound described herein, unless otherwise specified, A₂ (whenpresent) may be, for example, substituted or unsubstituted aryl orheteroaryl groups, such as C₆-C₃₀ substituted or unsubstituted aryl orheteroaryl groups, C₆-C₂₀ substituted or unsubstituted aryl orheteroaryl groups, and C₆-C₁₀ substituted or unsubstituted aryl orheteroaryl groups. Examples of such groups include, but are not limitedto, thiophene, pyrrole, furan, phenyl, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole andcarbazole 9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl;

In any compound described herein, unless otherwise specified, B₁ may besubstituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.

In any compound described herein, unless otherwise specified, Q may besubstituted or unsubstituted aryl or heteroaryl groups, such as C₆-C₃₀substituted or unsubstituted aryl or heteroaryl groups, C₆-C₂₀substituted or unsubstituted aryl or heteroaryl groups, and C₆-C₁₀substituted or unsubstituted aryl or heteroaryl groups. Examples of arylor heteroaryl groups include, but are not limited to, thiophene,pyrrole, furan, phenyl, phosphole, benzodithiophene, spirofluorene,spirothiophene, bithiophene, terthiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, thiazolyl, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, carbazole,9,9-RR′-9H-fluorene, 9-R-9H-carbazole,3,3′-RR′silylene-2,2′-bithiophene,3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene, where R and R′═C₁-C₃₀alkyl or C₆-C₃₀ aryl.

In some embodiments, the non-polymeric molecules described herein have asolubility of at least about 0.1 mg/mL in an organic solvent, 1 mg/mL inan organic solvent, 5 mg/mL, 10 mg/mL in an organic solvent, 30 mg/mL inan organic solvent, or 100 mg/mL in an organic solvent. The organicsolvent can be for example, chloroform, toluene, chlorobenzene,methylene dichloride, tetrahydrofuran, or carbon disulfide.

Preparation

Compounds may be prepared using methods available to a chemist ofordinary skill. In short, compounds of the invention may be assembled bymetal-catalyzed (including palladium-catalyzed) cross-coupling reactionsbetween aromatic precursors. Suitable aromatic precursors include thosebearing halogen substituents, which can be reacted with, for example,boronic acid or borane substituted aromatic compounds (Suzuki coupling),alkyl stannane substituted aromatic compounds (Stile coupling),alkysilane substituted aromatic compounds (Hiyama coupling), zincsubstituted aromatic compounds (Negishi coupling), among others.

An example preparation is shown in the Examples below.

Device Architectures, Materials, and Fabrication

Embodiments of the invention include electronic devices comprising anon-polymer compound comprising one or more groups of Formula A:

where M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), —N(R₁)—, —C(R₂)₂—C(R₃)₂—, —CR₂═CR₃—, —S(═O)₂—, —S(═O)—,—C(═O)—, —C(═S)—, or —C(═N—R₁)—; R₁ is H or a substituent; R₂ is H or asubstituent; and R₃ is H or a substituent. X₁ is H or halogen and Y₁ isH or halogen, where at least one of X₁ and Y₁ is halogen. In someembodiments, Formula A is a benzothiadiazole group, benzooxadizaolegroup, or benzotriazole group. In some embodiments, both X₁ and Y₁ arehalogen. In some embodiments, both X₁ and Y₁ are fluorine.

Embodiments of the invention include organic electronic devicescomprising any compound of formula B, as described herein.

In some embodiments, the electronic device is a solar cell. In manysolar cells, light passes though a transparent first electrode (such asITO-coated glass), is absorbed by a donor:acceptor mixture, whichresults in the separation of electrical charges and migration of thecharges to the electrodes, yielding a usable electrical potential.

Any electronic device described herein may have, for example, a firstelectrode, a second electrode and an active layer between the first andsecond electrode, where the active layer comprises the non-polymericcompound incorporating one or more groups of formula A or any compoundaccording to formula B, described herein.

The first electrode may be made of materials such as, but not limitedto, indium-tin oxide, indium-magnesium oxide, cadmium tin-oxide, tinoxide, aluminum- or indium-doped zinc oxide, gold, silver, nickel,palladium and platinum. In some embodiments, the first electrode has ahigh work function (4.3 eV or higher).

One electrode may be deposited onto a substrate. For example, the firstelectrode can be deposited onto a substrate, and the device can befabricated by subsequent deposition of layers. However, the secondelectrode can be deposited onto a substrate, with subsequent depositionof layers. In some embodiments, the substrate may be transparent. Thetransparent substrate can be glass, plastic, or any other transparentmaterial compatible with the electrode formed on the substrate.

The second electrode may be, for example, a metal electrode. Conductingmetal oxides, such as indium tin oxide, zinc oxide, or cadmium oxide,can also be used as electrodes, as well as conducting organic materials,such as electrodes comprising graphene. For metal electrodes, the metalmay be, for example, aluminum, silver or magnesium, but may be anymetal. Nanowires such as silver nanowires or other nanostructuredmaterials can also be used. If a transparent electrode is desired, verythin metallic layers of metals can also be used. In some embodiments,the device is annealed before and/or after evaporation of the metalelectrode.

In any electronic device, one electrode may be transparent. For example,the first electrode may be transparent, allowing light to enter thedevice, but in some embodiments, the second electrode can betransparent. In some embodiments, both electrodes are transparent. Insome embodiments, the transparent electrode may be indium tin oxide(ITO) coated onto a transparent substrate.

Any device may further include an electron-blocking, exciton-blocking,or hole-transporting layer. The electron-blocking, exciton-blocking orhole-transporting layer may be adjacent to the first electrode. In someembodiments, the hole transporting layer may be, for example,poly(3,4-ethylene dioxythiophene:poly(styrenesulfonate) (PEDOT:PSS).Other hole transporting materials, such as polyaniline (with suitabledopants), orN,N′-diphenyl-N,N′-bis(3-methylphenyl)[1,1′-biphenyl]-4,4′-diamine(TPD), nickel oxide, can be used.

In some embodiments, the layer may be an electron-blocking,exciton-blocking, or hole-transporting metal oxide. Electron-blocking,exciton-blocking, or hole-transporting metal oxides include, forexample, MoO₃, MoO_(3-x), V₂O_(5-x), NiO, Ta₂O₅, Ag₂O, CuO, Cu₂O,CrO_(3-x), and WO₃, where x is between 0.01 and 0.99, or between 0.1 and0.9. Other suitable materials are described in Greiner, Mark T. et al.,“Universal energy-level alignment of molecules on metal oxides,” NatureMaterials, DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

Any device may further include a hole-blocking, exciton-blocking, orelectron-transporting layer. In some embodiments, this layer is adjacentto the second electrode, and may optionally be deposited on top of thedonor-acceptor film in order to block holes or excitons, act as anoptical buffer, or otherwise benefit the electrical characteristics ofthe device. 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline can act as ahole-blocking or exciton-blocking material, while4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine andpolyethylene dioxythiophene can act as exciton-blocking materials. Othermaterials that can be used between the second electrode and the activelayer are titanium suboxide, ZnO, Cs₂CO₃, and ZrO₃. Additional materialssuitable for use are described in Greiner, Mark T. et al., “Universalenergy-level alignment of molecules on metal oxides,” Nature Materials,DOI: 10.1038/NMAT3159 (Nov. 6, 2011).

In any device, the active layer may further include an electronacceptor. The electron acceptor may be, for example, a fullerene such as[6,6]-phenyl C61-butyric acid methyl ester (PCBM), but may be adifferent fullerene (including, but not limited to, C71-PCBM), atetracyanoquinodimethane, a vinazene, a perylene tetracarboxylicacid-dianhydride, a perylene tetracarboxylic acid-diimide, anoxadiazole, carbon nanotubes, or any other organic electron acceptor,such as those compounds disclosed in U.S. 2008/0315187.

In other embodiments, the electron acceptor is an inorganic acceptorselected from TiO₂ (titanium dioxide), TiO_(x) (titanium suboxide, wherex<2) and ZnO (zinc oxide). The titanium dioxide can be anatase, rutile,or amorphous. A titanium dioxide layer can be prepared by depositing asol-gel precursor solution, for example by spincasting or doctorblading,and sintering at a temperature between about 300° C. and 500° C. When aninorganic layer is used, component (c) of the optoelectronic devicedescribed above can be comprised of a layer of electron-donatingchromophores of the general Formula I-VII and an inorganicelectron-acceptor layer. Alternatively, the inorganic material can bedispersed in the electron-donating chromophores to create a singlelayer. Preparation of TiO₂ for use in solar cells is described in BrianO'Regan & Michael Grätzel, Nature 353:737 (1991) and Serap Günes et al.,2008 Nanotechnology 19 424009.

When titanium suboxide according to the formula TiO_(x) where x<2, isused, x may follow the following relationships: 1<x<1.98, 1.1<x<1.9,1.2<x<1.8, or 1.3<x<1.8. X in the formula TiO_(x) can be, for example,<2, <1.98, <1.9, <1.8, <1.7, or <1.6.

In some embodiments, the device further includes a dielectric layer.

In some embodiments, the device further includes a third electrode.

Some devices may be tandem solar cells, such as those disclosed in US2009/0126779. Tandem solar cells are arranged so that light which is notabsorbed by a first solar cell passes to a second solar cell, where thesecond solar cell may have a smaller bandgap than the first solar cellin order to absorb electromagnetic radiation that cannot be usefullyabsorbed by the first solar cell.

Some devices may include passivating layers, such as those disclosed inUS 2007/0221926 and US 2007/0169816.

Some devices may include optical spacer layers, such as those disclosedin US 2006/0292736.

One method of fabricating the optoelectronic device is as follows: Aconductive, transparent substrate is prepared from commerciallyavailable indium tin oxide-coated glass and polystyrenesulfonic aciddoped polyethylenedioxythiophene using standard procedures. A solutioncontaining a mixture of the donor and acceptor materials is prepared sothat the ratio of donor to acceptor is between 1:99 and 99:1 parts bymass; or in some embodiments between 3:7 and 7:3 parts by mass. Theoverall concentration of the solution may range between 0.1 mg/mL and100 mg/mL, but the range of 10 mg/mL and 30 mg/mL is particularlysuitable for some embodiments. Non-polymeric molecules are used thathave a solubility of at least about 0.1 mg/mL in an organic solvent, 1mg/mL in an organic solvent, 5 mg/mL, 10 mg/mL in an organic solvent, 30mg/mL in an organic solvent, or 100 mg/mL in an organic solvent. Theorganic solvent can be selected from chloroform, toluene, chlorobenzene,methylene dichloride, tetrahydrofuran, or carbon disulfide.

Useful solvents include chloroform, toluene, chlorobenzene, methylenedichloride, tetrahydrofuran, and carbon disulfide. However, the solventused may be any solvent which dissolves or partially dissolve both donorand acceptor materials and has a non-zero vapor pressure.

The solution of donor and acceptor is deposited by spin casting,doctor-blading, ink-jet printing, roll-to-roll coating, slot-dyecoating, gravure coating, or any process which yields a continuous filmof the donor-acceptor mixture such that the thickness of the film iswithin the range of 10 to 1000 nm, or between 50 and 150 nm in someembodiments.

In some embodiments, the layer of the donor and acceptor is cast from asolution comprising a solvent and the electron donor and the electronacceptor. The solvent can comprise chloroform, thiophene,trichloroethylene, chlorobenzene, carbon disulfide, a mixture of any ofthe foregoing solvents or any solvent or solvent mixture that dissolvesboth the donor and acceptor organic small molecule. The solvent can alsoinclude processing additives, such as those disclosed in US PatentApplication Publication Nos. 2009/0032808, 2008/0315187, or2009/0108255. For example, 1,8-diiodooctane (DIO) can be added to thesolvent/donor/acceptor mixture in an amount of 0.1-10% by volume. Theadditive, such as 2% DIO, can be added to any organic solvent used tocast the layer of donor/acceptor, such as chloroform. The solvent canalso include doping agents such as molybdenum trioxide (MoO₃). Forexample, MoO₃ can be added to the solvent/donor/acceptor mixture in anamount of 0.1-10% by volume.

Finally, an electrode, such as a metal electrode, is deposited on top ofthe structure by thermal evaporation, sputtering, printing, laminationor some other process. Conducting metal oxides, such as indium tinoxide, zinc oxide, or cadmium oxide, can also be used as electrodes, aswell as conducting organic materials, such as electrodes comprisinggraphene. For metal electrodes, the metal can be, for example, aluminum,silver or magnesium, but may be any metal. Nanowires such as silvernanowires or other nanostructures can also be used. If a transparentelectrode is desired, very thin metallic sheets of metals can also beused. In some embodiments, the device is annealed before and/or afterevaporation of the metal electrode.

Hole and electron mobilities are important parameters to consider in thefabrication/function of bulk heterojunction solar cells. For optimaldevice performance, a balance in the mobility of both charge carriers isdesirable. The electron and hole mobilities may both be on the order of10⁻⁴ cm²/Vs or higher. In some embodiments, the electron mobilities areon the order of 10⁻³ cm²/Vs or higher. In some embodiments, the electronmobilities are on the order of 10⁻⁴ cm²/Vs or higher, and the holemobilities are between 10⁻⁸ cm²/Vs and 10⁻⁴ cm²/Vs or higher. In otherembodiments, the electron mobilities are on the order of 10⁻³ cm²/Vs orhigher, and the hole mobilities are between 10⁻⁸ cm²/Vs and 10⁻⁴ cm²/Vsor higher.

Optoelectronic devices of the present invention have excellentphotovoltaic properties. In some embodiments, the power conversionefficiency (PCE) is at least 0.5%, at least 1.0%, at least 2.0%, or atleast 3.0%. In some embodiments, the short circuit current density isgreater than 3.0 mA/cm², but may be greater than 8 mA/cm² in someembodiments. In some embodiments, the open circuit voltage is between0.3 and 1.0 V or higher. In some embodiments, the device exhibits anexternal quantum efficiency of approximately 35% or greater between 300and 800 nm.

The morphological properties of the donor:acceptor films can be measuredusing atomic force microscopy or other surface-sensitive techniques. Thefilms may have, for example, a root-mean-squared surface roughness ofless than 1.0 nm or less than 0.5 nm in some embodiments.

For embodiments of the devices using an inverted device architecture,the first electrode can comprise Au or another material having a workfunction higher than the work function of the second electrode, whilethe second electrode can comprise an ITO substrate modified using aself-assembled monolayer of 3-aminopropyltrimethoxysiloxane or anothermaterial having a work function lower than the work function of thefirst electrode.

FIG. 3 provides a schematic illustration of an electronic oroptoelectronic device 100 according to an embodiments of the currentinvention. The electronic or optoelectronic device 100 has a firstelectrode 102, a second electrode 104, spaced apart from said firstelectrode 102, and an active layer between said first electrode 102 andsaid second electrode 104. The active layer 106 can include anynon-polymeric compound of formula A or formula B described herein. Thefirst electrode 102 may be, for example, a transparent anode ofindium-tin-oxide (ITO). The second electrode 104 may be, for example, ametal aluminum cathode.

In some embodiments, the electronic or optoelectronic device 100 caninclude a hole transporting layer 108 between the first electrode 102and the active layer 106. The hole transporting layer 108 can be, forexample, PEDOT:PSS. In some embodiments, the first electrode 102 can beformed on a substrate 110. The substrate 110 can be a transparentsubstrate in some embodiments. In some embodiments, the substrate 110can be glass.

EXAMPLES Example 1

Synthesis of 5,6-difluorobenzo[c][1,2,5]thiadiazole (F₂BT)

To a 500 mL two-necked round bottom flask were added4,5-difluorobenzene-1,2-diamine (10.0 g, 0.070 mol, Matrix Scientific),anhydrous CHCl₃ (250 mL) and anhydrous triethylamine (40 mL, 0.28 mol).The solution was stirred until the diamine was completely dissolved.Thionyl chloride (SOCl₂, 10.5 mL, 0.145 mol) was added dropwise using anaddition funnel and the mixture heated to reflux for 5 h. The mixturewas then cooled to room temperature, poured into 500 mL of distilledH₂O, and then extracted with CH₂Cl₂ (100 mL×3). The collected organiclayers were combined and dried over MgSO₄. The solvent was removed invacuo and the resulting crude product purified by column chromatographyusing hexane/ethyl acetate (1:4) as eluent. After removal of solvent theproduct was obtained as brownish-white crystalline solid. Recoveredyield: 10.65 g (90%). 1H NMR (600 MHz, CDCl₃): δ 7.73 (t, 2H,J_(F-H)=12.0 Hz, 12.0 Hz).

Synthesis of 5,6-difluoro-4,7-diiodobenzo[c][1,2,5]thiadiazole (I₂F₂BT)

in a 500 mL two-necked round-bottom flask A mixture of 2 (2.70 g, 15mmol) I₂ (15 g, 60 mmol) and fuming sulfuric acid (75 mL) was stirred at60° C. for 24 hours. After cooling to room temperature, the reactionmixture was slowly poured into a 500 mL beaker with crushed ice.Chloroform (CHCl₃) was added and the mixture was transferred into a 1 Lseparatory funnel and washed with distilled water (150 mL×3), followedby 1M NaOH solution several times to remove excess iodine and finallywashed with saturated NaHCO₃. The organic layer was then dried overMgSO₄. After the filtration and solvent removal, the yellow paper-likesolid product was used without further purification. Recovered yield:3.52 g (52.6%).

Synthesis of7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(5,6-difluoro-4-iodobenzo[c][1,2,5]thiadiazole)

In 250 ml two-necked round bottom flask5,5′-bis(trimethylstannyl)-3,3′-Di-2-ethylhexylsilylene-2,2′-bithiophene(Me₃Sn-SDT_(EH)-SnMe₃, 2.0 gram, 2.68 mmol),5,6-difluoro-4,7-diiodobenzo[c][1,2,5]thiadiazole (I₂F₂BT, 2.30 g, 5.5mmol) were dissolved in anhydrous toluene (60 ml) and the resultingmixture degassed for 15 minutes. Pd(PPh₃)₄ (310 mg, 0.268 mmol, 10 mol%) was then added and the mixture degassed for another 2 minutes afterwhich it was heated to 110° C. for 16 hours under N₂ gas. Upon coolingto room temperature, the volatiles were removed in vacuo to give thecrude product as a dark reddish-brown solid. 100 ml of acetone was addedto crude product and the mixture stirred for 30 minutes and the solidsfiltered. The material was then loaded onto silica and purified by flashchromatography using CH₂Cl₂ as eluent. After fraction collection andsolvent removal a purplish red solid was obtained. The solid wasslurried in acetone (200 mL), stirred for 30 minutes, and filtered. Thesolid was washed with copious amounts of acetone and then dried undervacuum for 24 hours. The product was collected as dark reddish-maroonsolid. Recovered yield: 1.8 g (66%). ¹H NMR (600 MHz, CDCl₃): 7.54 (dt,2H, SDT-CH), 2.81 (m, ³J_(H-H)=7 Hz, 4H, Th—CH₂), 1.70 (m, ³J_(H-H)=7Hz, 4H, CH), 1.60 (m, 2H, CH), 1.40 (m, 4H, CH₂), 1.34 (m, 14H, CH₂),1.27 (m, 10H, CH₂), 1.15 (m, 4H, SiCH₂), 0.91 (m, 8H, CH₃), 0.87 (m,10H, CH₃).

Synthesis of7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(5,6-difluoro-4-(5′-hexyl-[2,2′-bithiophen]-5-yl)benzo[c][1,2,5]thiadiazole)

In 250 two-necked round bottom flask7,7′-(4,4-bis(2-ethylhexyl)-4H-silolo[3,2-b:4,5-b′]dithiophene-2,6-diyl)bis(5,6-difluoro-4-iodobenzo[c][1,2,5]thiadiazole)(IF₂BT-SDT_(EH)-IF₂BT, 1.5 grams, 1.48 mmol) and5′-Hexyl-2,2′-bithiophene-5-boronic acid pinacol ester (773 mg, 3.26mmol) were dissolved in anhydrous toluene (60 mL), and degassed for 15minutes. To this mixture was added Pd₂dba₃ (140 mg, 0.153 mmol, 10 mol%) and H⁺P(t-Bu₃)BF₄ ⁻ (180 mg, 0.620 mmol, 40 mol %) and the mixturethen degassed for another 2 minutes. Finally, degassed 2M K₂CO₃ (20 mL)was added and the mixture heated to 110° C. for 16 hours under N₂. Uponcooling the reaction mixture was poured into methanol (MeOH, 300 mL) andstirred for 30 minutes. The precipitate that formed was collect byfiltration and washed with copious amounts of MeOH and distilled H₂O.The crude product was first purified by flash chromatography using withmethylene chloride (CH₂Cl₂) as eluent. After fraction collection andsolvent removal a maroon solid was obtained. The product was thenfurther purified by soxhlet extraction with methanol and acetone toremoved monomers and catalyst residues. The remaining solid in thethimble was stirred in 50 ml of diethyl ether for 30 minutes, filteredand then dried under vacuum for 24 hours. The product (NET4C-F2) wascollected as a maroon solid. Recovered yield: 0.620 g (33%). ¹H NMR (600MHz, CDCl₃): δ 8.33 (t, 2H, J_(F-H)=7.2 Hz, SDT-CH), 8.18 (d,³J_(H-H)=3.6 Hz, 2H, Th—CH), 7.21 (d, ³J_(H-H)=6 Hz, 2H Th—CH), 7.13 (d,³J_(H-H)=6 Hz, 2H Th—CH), 6.72 (d, ³J_(H-H)=5 Hz, 2H Th—CH), 2.81 (m,³J_(H-H)=7 Hz, 4H Th—CH₂), 1.70 (h, ³J_(H-H)=7 Hz, 4H, CH), 1.60 (m, 2H,CH), 1.40 (m, 4H, CH₂), 1.34 (m, 14H, CH₂), 1.27 (m, 10H, CH₂), 1.15 (m,4H, SiCH₂), 0.91 (m, 8H, CH₃), 0.87 (m, 10H, CH₃).

Example 2—Determination of HOMO-LUMO Values

Calculations:

All calculations were performed using the Spartan '10 program. Optimizedgas-phase structures were obtained using the density functional theory(DFT) method B3LYP in conjunction with 6-31G(d,p) basis set, i.e.,B3LYP/6-31G(d,p).

FIG. 1 shows highest occupied molecular orbital (HOMO) and lowestunoccupied molecular orbital (LUMO) values calculated using the methodabove.

Example 3—General Procedures for Fabrication of Devices

Device Fabrication:

Solar cells were fabricated on patterned ITO-coated glass substrates.The ITO-coated glass substrates were first cleaned with detergent,ultrasonicated in water, acetone and isopropyl alcohol, and subsequentlydried overnight in an oven. MoO₃ films were thermally evaporated ontoUV-Ozone cleaned ITO substrates at a rate of 0.1 Å s⁻¹ under a vacuum ofabout 1×10⁻⁶ torr. The thickness of the MoO₃ film is approximately 13nm. A solution containing a mixture of NET4C-F2:[70]PCBM inchlorobenzene at a total solids concentration of 35 mg ml⁻¹ wasspin-cast on top of the MoO₃ films at a spin speed of 1500 rpm. Thecomposition of the active layer includes a 60:40 ratio ofNET4C-F2:[70]PCBM with and without 1,8-diiodooctane.

In other devices, PEDOT:PSS 4083 was spin cast onto UV-ozone cleaned ITOthen thermally annealed for 30 m at 150° C. The solution containing amixture of NET4C-F2:[70]PCBM in chlorobenzene at a total solidsconcentration of 35 mg ml⁻¹ was spin-cast on top of the PEDOT:PSS filmsat a spin speed of 1500 rpm with the same composition as previouslydescribed.

The active layers were heated at 70° C. for 10 min to evaporate anyresidual solvent. Finally, the aluminum cathode (˜100 nm) was depositedthrough a shadow mask by thermal evaporation under a vacuum of about1×10⁻⁶ torr. The active area of the device was 15.28 mm². The deviceswere finally annealed at 90° C. for 2 m.

Device Testing.

Current density-voltage (J-V) characteristics were measured using aKeithley 2602A Source Measure Unit while illuminated with a simulated100 mWcm⁻² AM 1.5G light source using a 300 W Xe arc lamp with an AM1.5global filter. Solar-simulator illumination intensity was measured usinga standard silicon photovoltaic with a protective KG1 filter calibratedby the National Renewable Energy Laboratory.

For organic photovoltaic devices, the overall PCE is determined by theequation:PCE=(Voc*Jsc*FF)/Pinwhere Voc is the open circuit voltage, Jsc is the short-circuit currentdensity, FF is the fill factor and Pin is the incident light power. Vocis the voltage at which there is no current flow in the device while theJsc is the amount of current flowing when no voltage is applied. Valuesare derived from the graph shown in FIG. 4 and are represented in thetable below.

DEVICE Voc (V) Jsc (mA/cm²) FF PCE PEDOT No Additive 0.88 −6.95 0.422.57% PEDOT 0.25% DIO 0.88 −6.95 0.49 2.98% MoO3 No Additive 0.88 −7.870.46 3.20% MoO3 0.25% DIO 0.88 −7.64 0.50 3.38%

Dsc Measurements.

Thermal analysis was performed using a differential scanning calorimeter(DSC (Perkin Elmer DSC 6000). A 2.2 mg sample was weighed into analuminum calorimetry pan and hermetically sealed. The sample wasanalyzed (3 sets of heating and cooling cycles) at a scan rate of 10°C./min. FIG. 7 shows data from the third heating/cooling cycle.

The disclosures of all publications, patents, patent applications andpublished patent applications referred to herein by an identifyingcitation are hereby incorporated herein by reference in their entirety.

As described herein, all embodiments or subcombinations may be used incombination with all other embodiments or subcombinations, unlessmutually exclusive.

Although the foregoing invention has been described in some detail byway of illustration and example for purposes of clarity ofunderstanding, it is apparent to those skilled in the art that certainchanges and modifications will be practiced. Therefore, the descriptionand examples should not be construed as limiting the scope of theinvention.

As described herein, all embodiments or subcombinations may be used incombination with all other embodiments or subcombinations, unlessmutually exclusive.

The invention claimed is:
 1. A compound having Formula B:

wherein M is selected from sulfur (S), oxygen (O), selenium (Se),tellurium (Te), −N(R₁)—, −C(R₂)₂—C(R₃)₂—, and —CR₂=CR₃—; wherein X₁ is Hor halogen and Y₁ is H or halogen; wherein H₂ is

wherein p is 1, 2, or 3; wherein each X₂ is H or halogen and each Y₂ isH or halogen, wherein in at least one subunit, only one of X₁ and Y₁ oronly one of X₂ and Y₂ is halogen; wherein J₁ is a nonentity; wherein Qis a bivalent, trivalent, or tetravalent aryl or heteroaryl group;wherein H₁ and L₁ are independently selected from −A₁—B₂,

wherein each B₂ is independently selected from H and

wherein n is an integer between 0 and 5, inclusive and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 for each structure where m and noccur together; wherein A₁ is independently selected from substituted orunsubstituted aryl group,

substituted or unsubstituted heteroaryl group except thiophene, where A₂is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group; wherein each B₁ is asubstituted or unsubstituted thiophene; and wherein R₁, R₂, R₃, R₄ andR₅ are each independently H or a substituent.
 2. A compound according toclaim 1 having Formula II:


3. A compound according to claim 2 wherein B₁ is a substitutedthiophene.
 4. A compound according to claim 2, wherein Q isindependently selected from substituted or unsubstituted thiophene,pyrrole, furan, phosphole, benzodithiophene, spirofluorene,spirothiophene, thienothiophene, dithienothiophene, benzothiophene,isobenzothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadiene, silacyclopentadienebithiophene, indole, benzene,naphthalene, anthracene, perylene, indene, fluorene, pyrene, azulene,pyridine, oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole and

carbazole 9,9-RR′-9H-fluorene 9-R-9H-carbazole 3,3′ RR′silylene-2,2′-bithiophene and 3,3′RR′-cyclopenta[2,1-b:3,4-b′[dithiophene where R and R′=C₁-C₃₀ alkyl or C₆-C₃₀ aryl.
 5. A compoundaccording to claim 4, where Q is 3,3′-RR′ silylene-2,2′-bithiophene andR and R′ are both C₁-C₃₀ alkyl.
 6. A compound according to claim 5 whereQ is


7. A compound according to claim 6 where n+m=1.
 8. A compound accordingto claim 7 where B₁ is substituted thiophene.
 9. A compound according toclaim 8 where B₁ is alkyl substituted thiophene.
 10. A compoundaccording to claim 1 having Formula I

wherein Q is a bivalent aryl or heteroaryl group.
 11. A compoundaccording to claim 10, wherein Q is independently selected fromsubstituted or unsubstituted thiophene, pyrrole, furan, phosphole,benzodithiophene, spirofluorene, spirothiophene, thienothiophene,dithienothiophene, benzothiophene, isobenzothiophene, benzodithiophene,cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, dithienopyrrole, dithienophosphole, and-9,9

2,2′-bithiophene and 3,3′RR′-cyclopenta[2,1-b:3,4-b′]-dithiophene

where R and R′=C₁-C₃₀ alkyl or C₆-C₃₀ aryl.
 12. A compound according toclaim 10, wherein L₁ is −A₁-B₂ and each A₁ is selected from substitutedor unsubstituted pyrrole, furan, phosphole, benzodithiophene,spirofluorene, spirothiophene, bithiophene, terthiophene,thienothiophene, dithienothiophene, benzothiophene, isobenzothiophene,benzodithiophene, cyclopentadithiophene, silacyclopentadiene,silacyclopentadienebithiophene, indole, benzene, naphthalene,anthracene, perylene, indene, fluorene, pyrene, azulene, pyridine,oxazole, thiazole, thiazine, pyrimidine, pyrazine, imidazole,benzoxazole, benzoxadiazole, benzothiazole, benzimidazole, benzofuran,isobenzofuran, thiadiazole, perfluorylbenzene, and carbazole.
 13. Acompound according to claim 10, wherein H₁ and L₁ are


14. A compound according to claim 1, having Formula IV-V:

wherein X₃ is H or halogen and Y₃ is halogen or; wherein Q is atrivalent aryl or heteroaryl group; wherein each E₁ is J₁ and wherein L₃is selected from −A₁-B₂,

wherein B₂ is independently selected from H and

wherein n is an integer between 0 and 5, inclusive, and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 for each structure where m and noccur together; wherein A₁ is independently selected from substituted orunsubstituted aryl group,

substituted or unsubstituted heteroaryl group except thiophene, where A₂is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group; wherein each B₁ is asubstituted or unsubstituted thiophene; and wherein R₁, R₂, R₃, R₄ andR₅ are each independently H or a substituent.
 15. A compound accordingto claim 1, having Formula VI-VII:

where the moiety

is a tetravalent aryl or heteroaryl group selected from

(2, 2’,7,7′-yl-9,9′-spirobi[fluorene]),

(3,3′,7,7′-yl-5,5′-spirobi[dibenzo[b,d]silole]),

(2,2′,6,6′-yl-4,4″-spirobi[cyclopenta[1,2-b:5,4-b′]dithiophene]), or

(2,2′,6,6′-yl-4,4′-spirobi[silolo[3,2-b:4,5-bldithiophene]); wherein X₃is H or halogen and Y₃ is H or halogen; wherein X₄ is H or halogen andY₄ is H or halogen; wherein each F₁ is J₁ and wherein each L₄ isindependently selected from −A₁-B₂,

wherein each B₂ is independently selected from H and

wherein n is an integer between 0 and 5, inclusive, and m is an integerbetween 0 and 5, inclusive, and 1≤m+n≤5 for each structure where m and noccur together; wherein A₁ is independently selected from substituted orunsubstituted aryl group,

substituted or unsubstituted heteroaryl group except thiophene, where A2is independently a substituted or unsubstituted aryl group orsubstituted or unsubstituted heteroaryl group; wherein each B₁ is asubstituted or unsubstituted thiophene; and wherein R₁, R₂, R₃, R₄ andR₅ are each independently H or a substituent L₁.
 16. A compoundaccording to claim 15, of Formula VIa:


17. A compound according to claim 15, of Formula VIIa:


18. A compound according to claim 1 where R₁, R₂, R₃, R₄, and R₅, areeach independently selected from the group consisting of hydrogen,halogen, F, NO₂, CN, acyl, O-acyl, S-acyl, N-acyl, alkyl, haloalkyl,substituted or unsubstituted aryl, substituted or unsubstitutedheteroaryl, alkenyl, alkoxy, alkylthio, alkylamine, arylamine, andhydroxy.
 19. A compound according to claim 18 where at least one of R₁,R₂, R₃, R₄, or R₅ is alkyl.
 20. A compound according to claim 1 whereinX₁ or Y₁ is fluorine.
 21. A compound according to claim 1, wherein M isS.
 22. An electronic or optoelectronic device comprising a non-polymericcompound of claim
 1. 23. An electronic or optoelectronic devicecomprising a non-polymeric compound of claim
 2. 24. An electronic oroptoelectronic device comprising: a first electrode; a second electrodespaced apart from said first electrode; and an active layer between saidfirst electrode and said second electrode, wherein said active layercomprises a compound according to claim
 1. 25. An electronic oroptoelectronic device according to claim 24, further comprising a holetransporting layer between said first electrode and said active layer.26. A compound according to claim 1 wherein: wherein p is 1 wherein onlyone of X₁ and Y₁ and only one of X₂ and Y₂ is halogen; wherein J₁ is anonentity; wherein Q is a substituted or unsubstituteddithienothiophene, benzodithiophene, cyclopentadithiophene,silacyclopentadienebithiophene, anthracene, fluorene, dithienopyrrole,dithienophosphole, or carbazole.
 27. An electronic or optoelectronicdevice comprising a compound of claim
 10. 28. An electronic oroptoelectronic device according to claim 27, wherein said device is asolar cell.
 29. An electronic or optoelectronic device according toclaim 27, wherein M is selected from sulfur (S), oxygen (O), and -N(R₁).30. An electronic or optoelectronic device according to claim 27,wherein R₁ is H, alkyl, or haloalkyl.
 31. An electronic oroptoelectronic device according to claim 27 comprising a firstelectrode, a second electrode and an active layer between the first andsecond electrode, where the active layer comprises a compound of FormulaI.
 32. An electronic or optoelectronic device according to claim 31,where one electrode is transparent.
 33. An electronic or optoelectronicdevice according to claim 31, further comprising an electron-blocking,exciton-blocking, or hole-transporting layer.
 34. An electronic oroptoelectronic device according to claim 31, further comprising ahole-blocking, exciton-blocking, or electron-transporting layer.
 35. Anelectronic or optoelectronic device according to claim 31, where theactive layer further comprises an electron acceptor.
 36. An electronicor optoelectronic device according to claim 35, where the electronacceptor is a fullerene.
 37. An electronic or optoelectronic deviceaccording to claim 31, further comprising a dielectric layer.
 38. Anelectronic or optoelectronic device according to claim 31, furthercomprising a third electrode.